N-pyridinylsulfonyl-N&#39;-triazinylureas

ABSTRACT

N-Pyridinylsulfonyl-N&#39;-pyrimidinylureas and N-pyridinylsulfonyl-N&#39;-triazinylureas of the formula ##STR1## wherein E is nitrogen or the methine bridge, 
     Z is oxygen or sulfur, 
     R 4  is hydrogen or C 1  -C 4  alkyl, 
     R 5  and R 6  are each independently hydrogen, halogen, C 1  -C 4  alkyl, C 1  -C 4  haloalkyl, C 1  -C 4  alkoxy, C 1  -C 4  haloalkoxy, C 1  -C 4  alkylthio, C 3  -C 6  dialkoxyalkyl, C 1  -C 4  haloalkylthio, C 2  -C 4  -alkoxyalkyl, C 3  -C 6  cycloalkyl or --NR 12  R 13 , 
     G is a ##STR2## R 1  is hydrogen, halogen, nitro, C 1  -C 4  alkyl, C 1  -C 4  alkoxy, trifluoromethyl, trifluoromethoxy, difluoromethoxy, C 1  -C 4  alkyl carbonyl or --COOR 14 , 
     R 3  is a ##STR3##  group, n is 0, 1 or 2, 
     R 8  is hydrogen, C 1  -C 4  alkyl, C 1  -C 4  alkoxy, halogen, C 1  -C 4  haloalkyl, nitro, --COOR 14 , C 1  -C 4  haloalkoxy, --O--CR 15  R 16  --COOR 14  or --O--CR 15  R 16  --CN, 
     R 9  is hydrogen, halogen, C 1  -C 4  alkyl, C 1  -C 4  alkoxy, C 2  -C 4  alkoxyalkyl oder C 2  -C 4  alkoxyalkoxy, 
     R 10  and R 11  are each independently hydrogen or C 1  -C 4  alkyl, 
     R 12  and R 13  are each independently hydrogen or C 1  -C 4  alkyl, 
     R 14  is hydrogen, C 1  -C 4  alkyl, C 2  -C 4  alkenyl, C 3  -C 4  alkynyl, or is C 1  -C 4  alkyl which is substituted by C 1  -C 4  alkoxy, halogen or phenyl, and 
     R 15  and R 16  are each independently hydrogen or C 1  -C 4  alkyl, and the salts thereof have useful selective herbicidal properties for controlling weeds in crops of useful plants.

CROSS REFERENCE TO RELATED APPLICATIONS

This is a divisional of application Ser. No. 114,993, filed on Oct. 26,1987, now U.S. Pat. No. 4,875,923, which is a continuation-in-part ofapplication Ser. No. 719,614, filed on Apr. 3, 1985.

The present invention relates to novel sulfonylureas with herbicidal andplant growth regulalting properties, to the preparation thereof, tocompositions containing them as active ingredients, and to methods ofusing them for controlling weeds, preferably selectively, in crops ofuseful plants, or for regulating and inhibiting plant growth. Theinvention further relates to novel sulfonamides prepared asintermediates and to derivatives thereof.

The invention relates to sulfonylureas of the formula I ##STR4## whereinE is nitrogen or the methine bridge,

Z is oxygen or sulfur,

R⁴ is hydrogen or C₁ -C₄ alkyl,

R⁵ and R⁶ are each independently hydrogen, halogen, C₁ -C₄ alkyl, C₁ -C₄haloalkyl, C₁ -C₄ alkoxy, C₁ -C₄ haloalkoxy, C₁ -C₄ alkylthio, C₃ -C₆dialkoxyalkyl, C₁ -C₄ haloalkylthio, C₂ -C₄ -alkoxyalkyl, C₃ -C₆cycloalkyl or --NR¹² R¹³,

G is a ##STR5## R¹ is hydrogen, halogen, nitro, C₁ -C₄ alkyl, C₁ -C₄alkoxy, trifluoromethyl, trifluoromethoxy, difluoromethoxy, C₁ -C₄alkylcarbonyl or --COOR¹⁴,

R³ is a ##STR6## group, n is 0, 1 or 2,

R⁸ is hydrogen, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, halogen, C₁ -C₄ haloalkyl,nitro, --COOR¹⁴, C₁ -C₄ haloalkoxy, --O--CR¹⁵ R¹⁶ --COOR¹⁴ or --O--CR¹⁵R¹⁶ --CN,

R⁹ is hydrogen, halogen, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, C₂ -C₄ alkoxyalkyloder C₂ -C₄ alkoxyalkoxy,

R¹⁰ and R¹¹ are each independently hydrogen or C₁ -C₄ alkyl,

R¹² and R¹³ are each independently hydrogen or C₁ -C₄ alkyl,

R¹⁴ is hydrogen, C₁ -C₄ alkyl, C₂ -C₄ alkenyl, C₃ -C₄ alkynyl, or is C₁-C₄ alkyl which is substituted by C₁ -C₄ alkoxy, halogen or phenyl, and

R¹⁵ and R¹⁶ are each independently hydrogen or C₁ -C₄ alkyl,

and to the salts thereof.

Ureas, triazines and pyrimidines with herbicidal properties aregenerally known in the art. Sulfonylureas with herbicidal and plantgrowth regulating action have recently been described, for example inpublished European patent applications 39 239, 41 404, 45 196, 57 456,64 804 and 70 698.

In the above definitions, alkyl denotes straight chain or branchedalkyl, e.g. methyl, ethyl, n-propyl, isopropyl, or the four butylisomers.

Alkoxy denotes methoxy, ethoxy, n-propyloxy, isopropyloxy, or the fourbutyloxy isomers, with methoxy, ethoxy or isopropyloxy being preferred.

Alkylthio is e.g. methylthio, ethylthio, n-propylthio, isopropylthio, orthe four butylthio isomers, with methylthio and ethylthio beingpreferred.

Cycloalkyl is generally cyclopropyl, cyclobutyl, cyclopentyl orcyclohexyl.

Halogen itself or as moiety of a substituent such as haloalkoxy,haloalkylthio or haloalkyl is fluorine, chlorine and bromine, withfluorine and chlorine being preferred. Haloalkyl itself or as moiety ofhaloalkoxy or haloalkylthio is normally chloromethyl, fluoromethyl,difluoromethyl, trifluoromethyl, 2-chloroethyl, 2,2,2-trifluoroethyl,1,1,2,2-tetrafluoroethyl, pentafluoroethyl,1,1,2-trifluoro-2-chloroethyl, 2,2,2-trifluoro-1,1-dichloroethyl,pentachloroethyl, 3,3,3-trifluoropropyl, 2,3-dichloropropyl,1,1,2,3,3,3-hexafluoropropyl, with fluoromethyl, chloromethyl,difluoromethyl and trifluoromethyl being preferred.

Alkoxyalkyl is e.g. methoxymethyl, methoxyethyl, methoxypropyl,ethoxyethyl, ethoxymethyl or propyloxymethyl. Alkoxyalkoxy is e.g.methoxymethoxy, methoxyethoxy, methoxypropyloxy, ethoxymethoxy,ethoxyethoxy and propyloxymethoxy. Within the scope of the presentinvention, dialkoxyalkyl will generally be understood as meaning thefollowing radicals: dimethoxymethyl, 2,2-dimethoxyethyl,1,2-dimethoxyethyl, 1,2-diethoxyethyl, 2,2-diethoxyethyl,2,2-dimethoxypropyl, 3,3-dimethoxypropyl, 1,1-dimethoxyethyl,1,1-diethoxyethyl, 1,1-dimethoxypropyl, 2,3-dimethoxypropyl,1,1-dimethoxybutyl, 2,2-dimethoxybutyl, 3,3-dimethoxybutyl,4,4-dimethoxybutyl, with the geminal dialkoxyalkyl radicals, which mayalso be designated as acetals, being preferred.

Alkenyl radicals are vinyl, allyl, 2-butenyl, 3-butenyl or methallyl.Alkynyl is propargyl, 2-butynyl or 3-butynyl. Allyl and propargyl arepreferred.

Alkylcarbonyl radicals are in particular acetyl, propionyl, butyryl,isobutyryl, valeryl, isovaleryl or pivaloyl.

The invention also comprises the salts which the compounds of formula Iare able to form with amines, alkali metal bases and alkaline earthmetal bases, or with quaternary ammonium bases.

Preferred salt-forming alkali metal hydroxides and alkaline earth metalhydroxides are the hydroxides of lithium, sodium, potassium, magnesiumor calcium, most preferably those of sodium or potassium.

Examples of suitable salt-forming amines are primary, secondary andtertiary aliphatic and aromatic amines such as methylamine, ethylamine,propylamine, isopropylamine, the four butylamine isomers, dimethylamine,diethylamine, diethanolamine, dipropylamine, diisopropylamine,di-n-butylamine, pyrrolidine, piperidine, morpholine, trimethylamine,triethylamine, tripropylamine, quinuclidine, pyridine, quinoline andisoquinoline. Preferred amines are ethylamine, propylamine, diethylamineor triethylamine, with isopropylamine, diethanolamine and1,4-diazabicyclo[2.2.2]octane being most preferred.

Examples of quaternary ammonium bases are, in general, the cations ofhaloammonium salts, e.g. the tetramethylammonium cation, thetetraethylammonium cation, the trimethylethylammonium cation, and alsothe ammonium cation.

Among the compounds of formula I, those compounds are preferred whereineither

(a) Z is oxygen or

(b) R¹ is hydrogen, Cl, F, CH₃, C₂ H₅, CH₃ O, CF₃, CH₃ CO or

(c) R⁵ and R⁶ together contain not more than 4 carbon atoms and R⁴ ishydrogen or

(d) G is 3-phenylpyridin-2-yl.

A further preferred subgroup of compounds of formula I comprises thosecompounds wherein

Z is oxygen, R⁴ is hydrogen and G is 3-phenylpyridin-2-yl and R₅ and R₆together contain not more than 4 carbon atoms.

A preferred individual compound of formula I is:N-(3-phenylpyridin-2-ylsulfonyl)-N'-(4,6-dimethoxy-pyrimidin-2-yl)urea.

The preparation of the compounds of formula I is generally carried outby the following methods.

In accordance with a first process, the compounds of formula I areobtained by reacting a substituted sulfonamide of formula II

    G--SO.sub.2 --NH.sub.2                                     (II)

wherein G is as defined for formula I, with a carbamate of formula III##STR7## wherein E, R⁴, R⁵, R⁶ and Z are as defined for formula I and Ris phenyl, alkyl or substituted phenyl, in the presence of a base.

In accordance with a second process, the compounds of formula I areobtained by reacting a sulfonylcarbamate of formula IV ##STR8## whereinG and Z are as defined for formula I and R is phenyl, alkyl orsubstituted phenyl, with an amine of formula V ##STR9## wherein E, R⁴,R⁵ and R⁶ are as defined for formula I.

Finally, the compounds of formula I can also be obtained by reacting asulfonylisocyanate of formula VI

    G--SO.sub.2 --N═C═Z                                (VI)

wherein G and Z are as defined for formula I, with an amine of formula Vabove.

If desired, the resultant ureas of formula I can be converted intoaddition salts with amines, alkali metal hydroxides or alkaline earthmetal hydroxides or with quaternary ammonium bases. This is accomplishede.g. by reaction with the equimolar amount of base and by evaporatingoff the solvent.

It is convenient to carry out these reactions for obtaining compounds offormula I in aprotic, inert organic solvents. Examples of suuch solventsare hydrocarbons such as benzene, toluene, xylene or cyclohexane, carbontetrachloride, or chlorobenzene; ethers such as diethyl ether, ethyleneglycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuranor dioxane; nitriles such as acetonitrile or propionitrile; amides suchas dimethylformamide, diethylformamide or N-methylpyrrolidinone. Thereaction temperatures are preferably in the range from -20° C. to +120°C. The coupling reactions are normally slightly exothermic and can becarried out at room temperature. To shorten the reaction time or also toinitiate the reaction, it is expedient to heat the reaction mixturebriefly to boiling point. The reaction times can also be shortened byaddition of a few drops of a base as catalyst. Preferred bases aretertiary amines such as trimethylamine, triethylamine, quinuclidine,1,4-diazabicyclo[2.2.2]octane, 1,5-diazabicyclo[4.3.0]non-5-ene or1,8-diazabicyclo[5.4.0]undec-7-ene. However, the bases employed may alsobe inorganic bases, e.g. hydrides such as sodium hydride or calciumhydride, hydroxides such as sodium hydroxide or potassium hydroxide,carbonates such as sodium carbonate or potassium carbonate, orbicarbonates such as potassium bicarbonate or sodium bicarbonate.

The final products of formula I can be isolated by concentrating and/orevaporating off the solvent and purified by recrystallising ortriturating the solid residue in solvents in which they are not readilysoluble, e.g. an ether, an aromatic hydrocarbon or a chlorinatedhydrocarbon.

The intermediates of formulae II, IV and VI are novel. They have beenspecially developed for the synthesis of compounds of formula I andtherefore constitute a further object of the present invention.

The intermediates of formula II are prepared by processes known per se.Thus, for example, the compounds of formula II are obtained bydiazotising an amine of formula VII

    G--NH.sub.2                                                (VII)

wherein G is as defined for formula I, in hydrochloric acid, andreacting the diazo group with sulfur dioxide in the presence of acatalyst such as copper chloride and reacting the resultant sulfonylchloride of formula VIII

    G--SO.sub.2 --Cl                                           (VIII)

wherein G is as defined for formula I, with ammonia. The correspondingstarting amines are known or they can be obtained by known processes,e.g. by reduction from the corresponding nitro compounds.

Further, the compounds of formula II can be obtained by converting asulfonic acid of formula IX

    G--SO.sub.2 --OH                                           (IX)

wherein G is as defined for formula I, by treatment with a chlorinatingagent such as PCl₅, POCl₃, COCl₂ or SOCl₂, to give the correspondingsulfonyl chloride of formula VIII and reacting said chloride withammonia.

Likewise, the compounds of formula II can be obtained by treating abenzyl thioether of formula X

    G--S--CH.sub.2 --C.sub.6 H.sub.5                           (X)

wherein G is as defined for formula I, with chlorine and reacting theresultant sulfonyl chloride of formula VIII with ammonia.

In some cases the sulfonyl chlorides of formula VIII are obtained bydirect sulfochlorination of the substituted compound of formula XI

    G--H                                                       (XI)

wherein G is as defined for formula I, with chlorosulfonic acid ClSO₃ H.

The pyridinylsulfonylisocyanates of formula VI can be obtained e.g. byphosgenating the sulfonamides of formula II, in the presence of butylisocyanate and in an inert solvent, at reflux temperature. Similarreactions are described in "Neuere Methoden der praparativen organischemChemie", Band VI, 211-229, Verlag Chemie, Weinheim, 1970.

The isothiocyanates of formula VI are obtained by treating thesulfonamides of formula II with carbon disulfide and potassium hydroxideand subsequently phosgenating the dipotassium salt. Such processes aredescribed in Arch. Pharm. 229, 174 (1966).

The pyridinylsulfonylcarbamates of formula IV are obtained by reactingthe sulfonamides of formula II with a carbonate in the presence of abase. Similar processes are described in Japanese patent specification61 169.

The starting aminopyrimidines and aminotriazines of formula V andcorresponding carbamates of formula III are either known or they can beprepared by known methods from compounds disclosed in the literature.

The compounds of formulae VII, VIII, IX, X and XI are known or can beprepared by methods analogous to known ones.

The compounds of formula I are stable compounds and no precautionarymeasures are required for handling them.

When used at low rates of application, the compounds of formula I havegood selective growth inhibiting and selective herbicidal propertieswhich make them most suitable for use in crops of useful plants,preferably in cereals, cotton, soybeans and maize, and most preferablyin rice. In some cases damage is also caused to weeds which have onlybeen controlled up to now with total herbicides.

The mode of action of these compounds is unusual. Many aretranslocatable, i.e. they are absorbed by the plant and transported toother parts of it where they then exert their action. Thus, for example,it is possible to damage perennial weeds to the roots by surfacetreatment. Compared with other herbicides and growth regulators, thenovel compounds of formula I are effective even when used at very lowrates of application.

The compounds of formula I have in addition pronounced growthregulating, especially growth inhibiting, properties. The growth of bothmonocots and dicots is inhibited.

Thus, for example, the compounds of formula I selectively inhibit thegrowth of leguminosae which are frequently planted as cover crops intropical regions, so that, while soil erosion between cultivated plantsis prevented, the cover crops cannot compete with the cultivated plants.

Inhibition of the vegetative growth of many cultivated plants permitsmore plants to be sown in a crop area, so that a higher yield may beobtained per unit of area. A further mechanism of yield increase usinggrowth regulators resides in the fact that nutrients are ableincreasingly to promote flower formation and fruiting, whereasvegetative growth is inhibited.

At higher rates of application of compounds of formula I, all testedplants are so severely damaged in their development that they die.

The invention also relates to herbicidal and growth regulatingcompositions which contain a novel compound of formula I, and also tomethods of controlling weeds pre- and postemergence and of inhibitingthe growth of monocots and dicots, especially grasses, tropical covercrops and tobacco plant suckers.

The compounds of formula I are used in unmodified form or, preferably,together with the adjuvants conventionally employed in the art offormulation, and are therefore formulated in known manner toemulsifiable concentrates, directly sprayable or dilutable solutions,dilute emulsions, wettable powders, soluble powders, dusts, granulates,and also encapsulations in e.g. polymer substances. As with the natureof the compositions, the methods of applications, such as spraying,atomising, dusting, scattering or pouring, are chosen in accordance withthe intended objectives and the prevailing circumstances.

The formulations, i.e. the compositions, preparations or mixturescontaining the compound (active ingredient) of formula I and, whereappropriate, a solid or liquid adjuvant, are prepared in known manner,e.g. by homogeneously mixing and/or grinding the active ingredients withextenders, e.g. solvents, solid carriers and, where appropriate,surface-active compounds (surfactants).

Suitable solvents are: aromatic hydrocarbons, preferably the fractionscontaining 8 to 12 carbon atoms, e.g. xylene mixtures or substitutednaphthalenes, phthalates such as dibutyl phthalate or dioctyl phthalate,aliphatic hydrocarbons such as cyclohexane or paraffins, alcohols andglycols and their ethers and esters, such as ethanol, ethylene glycol,ethylene glycol monomethyl or monoethyl ether, ketones such ascyclohexanone, strongly polar solvents such as N-methyl-2-pyrrolidone,dimethylsulfoxide or dimethylformamide, as well as vegetable oils orepoxidised vegetable oils such as epoxidised coconut oil or soybean oil;or water.

The solid carriers used e.g. for dusts and dispersible powders arenormally natural mineral fillers such as calcite, talcum, kaolin,montmorillonite or attapulgite. In order to improve the physicalproperties it is also possible to add highly dispersed silicic acid orhighly dispersed absorbent polymers. Suitable granulated adsorptivecarriers are porous types, for example pumice, broken brick, sepioliteor bentonite; and suitable nonsorbent carriers are materials such ascalcite or sand. In addition, a great number of pregranulated materialsof inorganic or organic nature can be used, e.g. especially dolomite orpulverised plant residues.

Depending on the nature of the compound of formula I to be formulated,suitable surface-active compounds are nonionic, cationic and/or anionicsurfactants having good emulsifying, dispersing and wetting properties.The term "surfactants" will also be understood as comprising mixtures ofsurfactants.

Suitable anionic surfactants can be both water-soluble soaps andwater-soluble synthetic surface-active compounds.

Suitable soaps are the alkali metal salts, alkaline earth metal salts orunsubstituted or substituted ammonium salts of higher fatty acids (C₁₀-C₂₂), e.g. the sodium or potassium salts of oleic or stearic acid, orof natural fatty acid mixtures which can be obtained e.g. from coconutoil or tallow oil. Mention may also be made of fatty acid methyltaurinsalts.

More frequently, however, so-called synthetic surfactants are used,especially fatty sulfonates, fatty sulfates, sulfonated benzimidazolederivatives or alkylarylsulfonates.

The fatty sulfonates or sulfonates are usually in the form of alkalimetal salts, alkaline earth metal salts of unsubstituted or substitutedammonium salts and contain a C₈ -C₂₂ alkyl radical which also includesthe alkyl moiety of acyl radicals, e.g. the sodium or calcium salt oflignosulfonic acid, of dodecylsulfate or of a mixture of fatty alcoholsulfates obtained from natural fatty acids. These compounds alsocomprise the salts of sulfuric acid esters and sulfonic acids of fattyalcohol/ethylene oxide adducts. The sulfonated benzimidazole derivativespreferably contain 2 sulfonic acid groups and one fatty acid radicalcontaining 8 to 22 carbon atoms. Examples of alkylarylsulfonates are thesodium, calcium or triethanolamine salts of dodecylbenzene sulfonicacid, dibutylnaphthalenesulfonic acid, or of a naphthalenesulfonicacid/formaldehyde condensation product.

Also suitable are corresponding phosphates, e.g. salts of the phosphoricacid ester of an adduct of p-nonylphenol with 4 to 14 moles of ethyleneoxide, or phospholipids.

Non-ionic surfactants are preferably polyglycol ether derivatives ofaliphatic or cycloaliphatic alcohols, or saturated or unsaturated fattyacids and alkylphenols, said derivatives containing 3 to 10 glycol ethergroups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon moietyand 6 to 18 carbon atoms in the alkyl moiety of the alkylphenols.

Further suitable non-ionic surfactants are the water-soluble adducts ofpolyethylene oxide with polypropylene glycol,ethylenediaminopolypropylene glycol and alkylpolypropylene glycolcontaining 1 to 10 carbon atoms in the alkyl chain, which adductscontain 20 to 250 ethylene glycol ether groups and 10 to 100 propyleneglycol ether groups. These compounds usually contain 1 to 5 ethyleneglycol units per propylene glycol unit.

Representative examples of non-ionic surfactants arenonylphenolpolyethoxyethanols, castor oil polyglycol ethers,polypropylene/polyethylene oxide adducts,tributylphenoxypolyethoxyethanol, polyethylene glycol andoctylphenoxypolyethoxyethanol.

Fatty acid esters of polyoxyethylene sorbitan, such as polyoxyethylenesorbitan trioleate, are also suitable non-ionic surfactants.

Cationic surfactants are preferably quaternary ammonium salts whichcontain, as N-substituent, at least one C₈ -C₂₂ alkyl radical and, asfurther substituents, unsubstituted or halogenated lower alkyl, benzylor hydroxy-lower alkyl radicals. The salts are preferably in the form ofhalides, methylsulfates or ethylsulfates, e.g. stearyltrimethylammoniumchloride or benzyldi(2-chloroethyl)ethylammonium bromide.

The surfactants customarily employed in the art of formulation aredescribed e.g. in the following publications:

"McCutcheon's Detergents and Emulsifiers Annual", MC Publishing Corp.,Ridgewood, N.J., 1981; H. Stache, "Tensid-Taschenbuch", 2nd Edition, C.Hanser Verlag, Munich & Vienna, 1981; M. and J. Ash, "Encyclopedia ofSurfactants", Vol. I-III, Chemical Publishing Co., New York, 1980-81.

The herbicidal compositions usually contain 0.1 to 95%, preferably 0.1to 80%, of a compound of formula I, 1 to 99.9%, of a solid or liquidadjuvant, and 0 to 25%, preferably 0.1 to 25%, of a surfactant.

Preferred formulations are composed in particular of the followingconstituents (%=percentage by weight):

    ______________________________________                                        Emulsifiable concentrates                                                     active ingredient:                                                                           1 to 20%, preferably                                                                          5 to 10%                                       surfactant:    5 to 30%, preferably                                                                          10 to 20%                                      liquid carrier:                                                                              50 to 94%, preferably                                                                         70 to 85%                                      Dusts                                                                         active ingredient:                                                                           0.1 to 10%, preferably                                                                        0.1 to 1%                                      solid carrier: 99.9 to 90%, preferably                                                                       99.9 to 99%                                    Suspension concentrates                                                       active ingredient:                                                                           5 to 75%, preferably                                                                          10 to 50%                                      water:         94 to 24%, preferably                                                                         88 to 30%                                      surfactant:    1 to 40%, preferably                                                                          2 to 30%                                       Wettable powders                                                              active ingredient:                                                                           0.5 to 90%, preferably                                                                        1 to 80%                                       surfactant:    0.5 to 20%, preferably                                                                        1 to 15%                                       solid carrier: 5 to 95%, preferably                                                                          15 to 90%                                      Granulates                                                                    active ingredient:                                                                           0.5 to 30%, preferably                                                                        3 to 15%                                       solid carrier: 99.5 to 70%, preferably                                                                       97 to 85%.                                     ______________________________________                                    

Whereas commercial products will be preferably formulated asconcentrates, the end user will normally employ dilute formulations. Theformulations can be diluted to a concentration as low as 0.001% ofactive ingredient. The rates of application are normally from 0.01 to 10kg a.i./ha, preferably from 0.025 to 5 kg a.i./ha.

The compositions may also contain further ingredients such asstabilisers, antifoams, viscosity regulators, binders, tackifiers, aswell as fertilisers and other compounds for obtaining special effects.

Preparatory Examples:

EXAMPLE P1N-(3-Phenylpyridin-2-ylsulfonyl)-N'-(4,6-dimethoxypyrimidin-2-yl) urea(a) 2-Benzylthio-3-phenyl-pyridine

24.7 g of benzylmercaptane are solved in 450 ml of dimethylformamide andtreated with 27.7 g of potassium carbonate. To the resulting mixture37.9 g of 2-chloro-3-phenyl-pyridine are added dropwise. The mixture isheated to +80° C. for 20 hours, and then poured into ice-water. Theaqueous mixture is extracted twice with ethyl acetate. The combinedextracts are washed with water and brine, dried over magnesium sulfate,and concentrated. The resulting slurry is treated with petrol ether andthe crystalline precipitate is separate, yielding 34.7 g of2-benzylthio-3-phenyl-pyridine, melting at 99°-100° C.

(b) 3-Phenyl-pyridin-2-ylsulfonamide

15.4 g of 2-benzylthio-3-phenyl-pyridine are suspended in a mixture of135 ml of 36% hydrochloric acid and 33 ml of water. This suspension iscooled to a temperature between -5° C. and -10° C. and 14.7 g of gaseouschlorine at this temperature. The mixture is worked up by extracting thereaction mixture with methylene chloride. The organic extracts arewashed with water and brine, dried over magnesium sulfate andconcentrated. The residue is solved in 150 ml of tetrahydrofurane andcooled to a temperature between -10° C. and -15° C. Gaseous ammonia isblown onto the surface of the solution until the pH-value of thesolution is above 10. The mixture is agitated for a further 16 hours andthen concentrated. The residue is taken up with a mixture of ethylacetate and water and acidified by addition of hydrochloric acid. Theorganic phase is separated and the aqueous phase extracted once withethyl acetate. The combined organic phases are washed with water andbrine, dried over magnesium sulfate and concentrated. Recrystallisingthe residue from a ethyl acetate/petrolether-mixture yields 10,6 g of3-phenylpyridin-2-ylsulfonamide, melting at 172° C.

(c) 1.9 g of 3-phenyl-pyridin-2-ylsulfonylsulfonamide and 2.2 g ofN-(4,6-dimethoxy-pyrimidin-2-yl)-phenylcarbamat are dispersed in 40 mlof acetonitrile. A solution of 1.2 ml 1,8-diazabicyclo[5.4.0]undec-7-enein 5 ml of acetonitrile are added dropwise, whereby a clear solution isobtained. This reaction solution is kept at room temperature for 16hours. Then 0.7 ml of methanesulfonic acid and subsequently 15 ml ofice-water are added. A colourless precipitate is formed, which iscollected, washed with water and dried. The separated precipitate istreated with ether and dried, yielding 3.2 g ofN-(3-phenyl-pyridin-2-ylsulfonyl)-N'-(4,6-dimethoxypyrimidin)-2-yl)urea, having a melting point of 181° C. with decomposition.

The intermediates and final products listed in the following tables areprepared in analogous manner.

                  TABLE 1                                                         ______________________________________                                         ##STR10##                                                                                  Position                                                        Comp. W       SO.sub.2W R.sup.1                                                                             R.sup.3                                                                              physical data                            ______________________________________                                        1.01  NH.sub.2                                                                              2         H     3-phenyl                                                                             m.p. 172° C.                      1.02  NH.sub.2                                                                              2         H     3-benzyl                                        1.03  NH.sub.2                                                                              2         5-Cl  3-phenyl                                        1.04  NH.sub.2                                                                              3         2-Cl  6-phenyl                                        1.05  Cl      3         H     2-phenyl                                        1.06  Cl      3         5-Cl  2-phenyl                                        ______________________________________                                    

                                      TABLE 2                                     __________________________________________________________________________     ##STR11##                                                                        Position                    physical                                      Comp.                                                                             SO.sub.2                                                                            R.sup.1                                                                           R.sup.3                                                                            R.sup.4                                                                          R.sup.5                                                                           R.sup.6                                                                           E data                                          __________________________________________________________________________    2.01                                                                              2     H   3-phenyl                                                                           H  OCH.sub.3                                                                         OCH.sub.3                                                                         CH                                                                              m.p. 181° C.                           2.02                                                                              2     H   3-phenyl                                                                           H  OCH.sub.3                                                                         OCH.sub.3                                                                         N (decomp.)                                     2.03                                                                              2     H   3-phenyl                                                                           CH.sub.3                                                                         OCH.sub.3                                                                         OCH.sub.3                                                                         CH                                              2.04                                                                              2     H   3-benzyl                                                                           H  OCH.sub.3                                                                         OCH.sub.3                                                                         CH                                              2.05                                                                              2     5-Cl                                                                              3-phenyl                                                                           H  OCH.sub.3                                                                         OCH.sub.3                                                                         CH                                              2.06                                                                              2     5-Cl                                                                              3-phenyl                                                                           H  OCH.sub.3                                                                         OCH.sub.3                                                                         N                                               2.07                                                                              3     2-Cl                                                                              6-phenyl                                                                           H  OCH.sub.3                                                                         OCH.sub.3                                                                         CH                                              2.08                                                                              3     H   2-phenyl                                                                           H  CH.sub.3                                                                          OCH.sub.3                                                                         CH                                              2.09                                                                              3     H   2-phenyl                                                                           H  CH.sub.3                                                                          OCH.sub.3                                                                         N                                               __________________________________________________________________________

Formulation Examples

    ______________________________________                                         Example F1: Formulation Examples for compounds of formula I                  (percentages are by weight)                                                   (a) Wettable powders (a)     (b)     (c)                                      ______________________________________                                        compound of formula I                                                                              20%     50%     0.5%                                     sodium lignosulfonate                                                                              5%      5%      5%                                       sodium laurylsulfate 3%      --      --                                       sodium diisobutylnaphthalenesulfonate                                                              --      6%      6%                                       octylphenol polyethylene glycol ether                                                              --      2%      2%                                       (7-8 moles of ethylene oxide)                                                 highly dispersed silicic acid                                                                      5%      27%     27%                                      kaolin               67%     --      --                                       sodium chloride      --      --      59.5%                                    ______________________________________                                    

The active ingredient is thoroughly mixed with the adjuvants and themixture is thoroughly ground in a suitable mill, affording wettablepowders which can be diluted with water to give suspensions of thedesired concentration.

    ______________________________________                                        (b) Emulsifiable concentrate                                                                          (a)      (b)                                          ______________________________________                                        compound of formula I   10%      1%                                           octylphenol polyethylene glycol ether                                                                 3%       3%                                           (4-5 moles of ethylene oxide)                                                 calcium dodecylbenzenesulfonate                                                                       3%       3%                                           castor oil polyglycol ether                                                                           4%       4%                                           (36 moles of ethylene oxide)                                                  cyclohexanone           30%      10%                                          xylene mixture          50%      79%                                          ______________________________________                                    

Emulsions of any required concentration can be obtained from thisconcentrate by dilution with water.

    ______________________________________                                        (c) Dusts           (a)        (b)                                            ______________________________________                                        compound of formula I                                                                             0.1%       1%                                             talcum              99.9%      --                                             kaolin              --         99%                                            ______________________________________                                    

Dusts which are ready for use are obtained by mixing the activeingredient with the carriers, and grinding the mixture in a suitablemill.

    ______________________________________                                        (d) Extruder granulates                                                                            (a)       (b)                                            ______________________________________                                        compound of formula I                                                                              10%       1%                                             sodium lignosulfonate                                                                              2%        2%                                             carboxymethylcellulose                                                                             1%        1%                                             kaolin               87%       96%                                            ______________________________________                                    

The active ingredient is mixed and ground with the adjuvants, and themixture is subsequently moistened with water. The mixture is extrudedand then dried in a stream of air.

    ______________________________________                                        (e) Coated granulate                                                          ______________________________________                                        compound of formual I     3%                                                  polyethylene glycol (mol. wt. 200)                                                                      3%                                                  kaolin                    94%                                                 ______________________________________                                    

The finely ground active ingredient is uniformly applied, in a mixer, tothe kaolin moistened with polyethylene glycol. Non-dusty coatedgranulates are obtained in this manner.

    ______________________________________                                        (f) Suspension concentrate                                                                            (a)     (b)                                           ______________________________________                                        compound of formula I   40%     5%                                            ethylene glycol         10%     10%                                           nonylphenol polyethylene glycol ether                                                                 6%      1%                                            (15 moles of ethylene oxide)                                                  sodium lignosulfonate   10%     5%                                            carboxymethylcellulose  1%      1%                                            37% aqueous formaldehyde solution                                                                     0.2%    0.2%                                          silicone oil in the form of a 75%                                                                     0.8%    0.8%                                          aqueous emulsion                                                              water                   32%     77%                                           ______________________________________                                    

The finely ground active ingredient is intimately mixed with theadjuvants, giving a suspension concentrate from which suspensions of anydesired concentration can be obtained by dilution with water.

    ______________________________________                                        (g) Salt solution                                                             ______________________________________                                        compound of formula I      5%                                                 isopropylamine             1%                                                 octylphenol polyethylene glycol ether                                                                    3%                                                 (78 moles of ethylene oxide)                                                  water                      91%                                                ______________________________________                                    

Biological Examples

EXAMPLE B1 Preemergence herbicidal action

Plastic pots are filled with expanded vermiculite (density: 0.135 g/cm³,water-absorbing capacity: 0.565 l/l). After the nonadsorptivevermiculite has been saturated with an aqueous emulsion in deionisedwater which contains the test compound in a concentration of 70.8 ppm,seeds of the following plants are sown on the surface: Nasturtiumofficinalis, Agrostis tenuis, Stellaria media and Digitaria sanguinalis.The pots are then kept in a climatic chamber at 20° C., an illuminationof about 20 klux and a relative humidity of 70%. During the germinatingphase of 4 to 5 days, the pots are covered with lightpermeable materialand watered with deionised water to increase the local humidity. Afterthe 5th day, 0.5% of a commercial liquid fertiliser (Greenzit®, exCiba-Geigy) is added to the water. The test is evaluated 12 days aftersowing and the action on the plants is assessed.

In this test the compounds of formula I show strong herbicidal activity.

EXAMPLE B2 Growth inhibition of tropical leguminous cover crops

The test plants (Centrosema plumieri and Centrosema pubescens) arereared until fully grown and then cut back to a height of 60 cm. Theplants are sprayed 7 days later with an aqueous emulsion of the testcompound. The test plants are kept at 70% relative humidity and 600 luxartificial light for 14 hours per day, at day temperatures of 27° C. andnight temperatures of 21° C. The test is evaluated 4 weeks afterapplication by assessing and weighing the new growth compared withcontrols and by determining the phytotoxicity.

In this test a marked reduction in new growth of the plants treated withcompounds of the formula I is observed (less than 20% of the new growthof untreated control plants), without damage being caused to the testplants.

EXAMPLE B3 Growth regulation of soybeans

Soybeans of the "Hark" variety are sown in plastic containers in anearth/peat/sand mixture (6:3:1). The containers are put into a climaticchamber and the plants develop to the 5-6 trefoil leaf stage after about5 weeks by optimum control of temperature, light, fertiliser addition,and watering. The plants are then sprayed with an aqueous mixture of acompound of formula I until thoroughly wetted. The concentrationcorresponds to up to 100 g a.i. per hectare. Evaluation is made about 5weeks after application. Compared with untreated controls, the compoundsof formula I markedly increase the number and weight of the harvestedsiliquae on the leading shoot.

EXAMPLE B4 Growth inhibition of cereals

Summer barley (Hordeum vulgare) and summer rye (Secale) are sown insterilised soil in plastic beakers in a greenhouse and watered asrequired. The cereal shoots are treated about 21 days after sowing withan aqueous spray mixture of a compound of the formula I. Theconcentration corresponds to up to 100 g of active ingredient perhectare. Evaluation of the growth of the cereals is made 21 days afterapplication. A comparison with untreated controls shows that the growthof cereal plants treated with compounds of formula I is reduced (60-90%of the controls) and that the diameter of the stalks has in some casesincreased.

EXAMPLE B5 Growth inhibition of grasses

Seeds of the grasses Lolium perenne, Poa pratensis, Festuca ovina,Dactylis glomerate and Cynodon dactylon are sown in plastic dishesfilled with an earth/peat/sand mixture (6:3:1), in a greenhouse, andwatered as required. The emergent grasses are cut back weekly to aheight of 4 cm, and about 50 days after sowing and 1 day after the lastcut are sprayed with an aqueous spray mixture of a compound of formulaI. The concentration of test compound corresponds to a rate ofapplication of up to 100 g a.i. per hectare. The growth of the grassesis evaluated 21 days after application. The compounds of formula Ieffect a reduction in new growth in the range of 10-30% in comparisonwith untreated controls.

EXAMPLE B6 Preemergence test

In a greenhoouse, seeds of the plants tested were sown in flower pots of12-15 cm diameter. Immediately after sowing, the surface of the soil wastreated with the aqueous dispersion of the compounds to be tested.Concentrations of 500, 125 of 30 g a.i./ha were employed. The pots werethen kept in the greenhouse at 22°-25° C. and 50-70% relative humidity.The test was evaluated 3 weeks later in accordance with the followingrating:

    ______________________________________                                        1:      plants have not emerged or are totally withered                       2-3:    very pronounced action                                                4-6:    medium action                                                         7-8:    weak action                                                           9:      no action (as untreated controls).                                    ______________________________________                                    

Preemergence action:

    ______________________________________                                        Dosage in g a.i./ha                                                                          Compound No. 2.01                                              plant tested   500        125     30                                          ______________________________________                                        wheat          5          8       9                                           bromus tectorum                                                                              1          2       5                                           echinochloa crus galli                                                                       2          4       8                                           sorghum halepense                                                                            2          3       8                                           abutilon       1          4       7                                           chenopodium sp.                                                                              1          2       4                                           solanum nigrum 2          3       4                                           galium aparine 2          2       3                                           ______________________________________                                    

What is claimed is:
 1. A sulfonylurea of formula I ##STR12## wherein Eis nitrogen,Z is oxygen or sulfur, R⁴ is hydrogen or C₁ -C₄ alkyl, R⁵and R⁶ are each independently hydrogen, halogen, C₁ -C₄ alkyl, C₁ -C₄haloalkyl, C₁ -C₄ alkoxy, C₁ -C₄ haloalkoxy, C₁ -C₄ alkylthio, C₃ -C₆dialkoxyalkyl, C₁ -C₄ haloalkylthio, C₂ -C₄ -alkoxyalkyl, C₃ -C₆cycloalkyl or --NR¹² R¹³, G is a ##STR13## R¹ is hydrogen, halogen,nitro, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, trifluoromethyl, trifluoromethoxy,difluoromethoxy, C₁ -C₄ alkyl carbonyl or --COOR¹⁴, R³ is a ##STR14##group, n is 0, 1 or 2, R⁸ is hydrogen, C₁ -C₄ alkyl, C₁ -C₄ alkoxy,halogen, C₁ -C₄ haloalkyl, nitro, --COOR¹⁴, C₁ -C₄ haloalkoxy, --O--CR¹⁵R¹⁶ -COOR¹⁴ or --O--CR¹⁵ R¹⁶ --CN, R⁹ is hydrogen, halogen, C₁ -C₄alkyl, C₁ -C₄ alkoxy, C₂ -C₄ alkoxyalkyl oder C₂ -C₄ alkoxyalkoxy, R¹⁰and R¹¹ are each independently hydrogen or C₁ -C₄ alkyl, R¹² and R¹³ areeach independently hydrogen or C₁ -C₄ alkyl, R¹⁴ is hydrogen, C₁ -C₄alkyl, C₂ -C₄ alkenyl, C₃ -C₄ alkynyl, or is C₁ -C₄ alkyl which issubstituted by C₁ -C₄ alkoxy, halogen or phenyl, and R¹⁵ and R¹⁶ areeach independently hydrogen or C₁ -C₄ alkyl, or a salt thereof.
 2. Acompound according to claim 1, wherein Z is oxygen.
 3. A compoundaccording to claim 1, wherein R¹ is hydrogen, Cl, F, CH₃, C₂ H₅, CH₃ O,CF₃ or CH₃ CO.
 4. A compound according to claim 1, wherein R⁵ and R⁶together contain not more than 4 carbon atoms and R⁴ is hydrogen.
 5. Acompound according to claim 1, wherein G is 3-phenylpyridin-2-yl.
 6. Acompound according to claim 1, wherein Z is oxygen, R⁴ is hydrogen and Gis 3-phenylpyridin-2-yl and R⁵ and R⁶ together contain not more than 4carbon atoms. 7.N-(3-Phenylpyridin-2-ylsulfonyl)-N'-(4,6-dimethoxy-1,3,5-triazin-2-yl)ureaaccording to claim
 1. 8. A herbicidal and plant growth inhibitingcomposition which contains, as active ingredient, an effective amount ofat least one substituted sulfonylurea of formula I according to claim 1,together with carriers and/or other adjuvants.
 9. A method ofcontrolling undesired plant growth, which method comprises applying tothe plants or to the locus thereof an effective amount of a compound offormula I according to claim 1, or of a composition containing such acompound.
 10. A method of inhibiting plant growth, which methodcomprises applying to the plants or to the locus thereof an effectiveamount of a compound of formula I according to claim 1, or of acomposition containing such a compound.
 11. A method of influencingplant growth for increasing yield, which method comprises applying tothe plants or to the locus thereof an effective amount of a compound offormula I according to claim 1, or of a composition containing such acompound.
 12. A method according to claim 9 of selectively controllingweeds pre- or postemergence in crops of useful plants.
 13. A methodaccording to claim 10 of suppressing plant growth beyond the 2-leafstage, which method comprises applying the active ingredientpreemergence.
 14. A method according to claim 12, wherein the crops arerice crops.